Oxime carbonetes as fungicidal or bactericidal agents

ABSTRACT

Compounds having the formula ##STR1## in which R is alkyl having from 1 to 6 carbon atoms. The compounds are useful in inhibiting the growth of bacteria and fungi.

This is a division of application Ser. No. 542,159, filed Jan. 20, 1975,now U.S. Pat. No. 3,988,357.

DESCRIPTION OF THE INVENTION

This invention relates to novel chemcial compounds and to their use incontrolling fungi and bacteria. More particularly, the chemicalcompounds are certain keto oxime carbonates.

The compounds of the present invention are those having the formula##STR2## in which R is alkyl having from 1 to 6 carbon atoms.

The compounds of the present invention can be prepared by reacting acompound of the formula ##STR3## with a compound of the formula ##STR4##in which halo is chlorine or bromine and R is as defined.

Preferably, the reaction is carried out in the presence of a base suchas pyridine and in a solvent for the reactants. Generally, the reactionis exothermic so no heating is required. Cooling is sometimes requiredto control the reaction rate. The compounds of this invention can berecovered from the mixture and purified by standard procedures.

Compounds of the formula ##STR5## CAN BE PREPARED BY REACTING ##STR6##WITH EXCESS HYDROXYLAMINE HYDROCHLORIDE OR HYDROXYLAMINE HYDROBROMIDE INETHANOL AND WATER. The reaction can be run with heating under reflux forseveral hours. The desired product is recovered and purified byconventional techniques.

EXAMPLE 1 1,3-dichloroacetoneoxime

63.5 GRAMS (0.50 MOLE) 1,3-DICHLOROPROPANONE, 69.5 GRAMS (1.00 MOLE)HYDROXYLAMINE HYDROCHLORIDE, 250 ML. ETHANOL AND 25 ML. OF WATER WERECOMBINED AND HEATED UNDER REFLUX FOR FOUR HOURS. The cooled mixture waspoured into 500 ml. of water. The aqueous solution was extracted withthree 100 ml. portions of chloroform The chloroform phases were combinedand dried with anhydrous MgSO₄. The chloroform was evaporated to give66.3 g. (93.6% theory) of 1,3-dichloroacetoneoxime, ##STR7## N_(D) ³⁰ =1.5044.

EXAMPLE 2 1,3-dichloroacetoneoxime O-methyl carbonate

14.1 GRAMS (0.10 MOLE) 1,3-DICHLOROACETONEOXIME, 10.1 GRAMS (0.13 MOLE)METHYLCHLOROFORMATE WERE COMBINED IN 200 ML. OF BENZENE. The mixture wasstirred with cooling at 13° to 14° C. for 20 minutes with 18.1 ml. (0.13mole) of triethyl amine. The mixture was allowed to warm to roomtemperature. The mixture was washed with two 100 ml. portions of water.The benzene phase was dried with anhydrous MgSO₄ and evaporated to give9.7 g. of 1,3-dichloroacetoneoxime O-methyl carbonate. ##STR8## N_(d) ³⁰= 1.4722.

The following is a table of certain selected compounds that arepreparable according to the procedure described hereto. Compound numbershave been assigned to each compound and are used throughout theremainder of the application.

    ______________________________________                                        Compound No.          R                                                       ______________________________________                                        1.sup.a               methyl                                                  2                     ethyl                                                   3                     n-butyl                                                 4                     hexyl                                                   ______________________________________                                         .sup.a Prepared in Example 2.?                                           

IN VITRO VIAL TEST

The following test illustrates utility of the compounds in controllingfungi and bacteria. This test measures the bactericidal and fungicidalproperties of a compound when in contact with a growing bacterium orfungus. The test is conducted by partially filling two 1-ounce vialswith malt broth and one 1-ounce vial with nutrient broth. Next the testcompound is added to the vials at a certain concentration, expressed inparts per million, and mixed with the broth. A water suspension ofspores of the desired fungi or cells of the desired bacteria (oneorganism per vial) is added. The vials are then sealed and incubated forone week; at this time the vials are examined and the results recorded.Table II shows the results of various compounds tested by the In VitroVial Test, partial control of the test organism is indicated byparenthesis. In such a case, complete control was observed at the nexthigher concentration.

                                      TABLE II                                    __________________________________________________________________________    Concentration (p.p.m.) Which Inhibited Growth                                 Compound                                                                            Aspergillus                                                                          Penicillium                                                                          Escherichia                                                                          Staphylococcus                                     number                                                                              niger  italicum                                                                             coli   aureus                                             __________________________________________________________________________    1     (.25)  (.25)  >50    25                                                 2     .125   (.125) >50     5                                                 3     .125   (1)    >50    25                                                 __________________________________________________________________________

SULFATE REDUCING BACTERIA IN VITRO TEST

This test measures the bactericidal properties of a compound when incontact with a sulfate reducing bacteria, specifically Desulfovibriodesulfuricans. The test is conducted by dissolving the test compound inacetone to give an 0.5% solution. This toxicant is added to vialscontaining sterile Sulfate API broth with tryptone under anaerobicconditions at such levels to give final toxicant concentrations of 1, 5,10 and 50 ug/ml. of solution. An inoculant solution of 0.5 ml. of thegrowing organism, Desulfovibrio desulfuricans, is added to the vialsfollowed by sufficient sterile distilled water to give a total of 10 ml.of solution in the vials. The vials are incubated at room temperaturefor 3 to 5 days until untreated controls show growth of the organism asindicated by the black color development in the vials.

The following is a summary of the minimum inhibitory concentrationnecessary to control the organism.

    ______________________________________                                        Compound Number                                                                             Minimum Inhibitory Conc. μg/ml                               ______________________________________                                        2             5                                                               ______________________________________                                    

As can be seen by the test results, the compounds find particularutility as bactericides and fungicides. The compounds can be applied ina variety of ways at various concentrations. They can be combined withsuitable carriers and applied as dusts, sprays, or drenches. The amountapplied will depend on the nature of the utility. The rate ofapplication can also vary with the microbiological use intended.

The problems associated with sulfate reducing bacteria and method ofapplication for the control thereof are described in U.S. Pat. No.3,300,375 which is incorporated herein by reference thereto.

It is claimed:
 1. A method of inhibiting the growth of bacteria whichcomprises applying thereto a bactericidally effective amount of acompound of the formula ##STR9## in which R is alkyl having 1 to 6carbon atoms.
 2. A method inhibiting the growth of fungi which comprisesapplying thereto a fungicidally effective amount of a compound of theformula ##STR10## in which R is alkyl having 1 to 6 carbon atoms.
 3. Amethod of inhibiting the growth of sulfate reducing bacterial whichcomprises contacting said bacteria with a bactericidally effectiveamount of a compound of the formula ##STR11## in which R is alkyl having1 to 6 carbon atoms.
 4. The method of claim 3 in which R is ethyl. 5.The method of claim 3 in which said bacteria is of the speciesDesulfovibrio.